Salts of new hardenable, basic, ternary condensation products



SALTS OF NEW HARDENABLE, BASIC, TERNARY CONDENSATION PRODUCTS OttoAlbrecht, Neuewelt, near Basel, and Armin Hiestand, Basel, Switzerland,assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing.Application January 7,1957 Serial No. 632,636

Claims. (Cl. 260-21) This is a continuation in part of U. S. Patentapplication Serial No. 304,442, filed August 14, 1952, now U. S. PatentNo. 2,783,231.

The present invention is based on the observation that Water-solublesalts, including quaternary ammonium salts of hardenable, basic ternarycondensation products are obtained when there are heated together (a) Amember selected from the group consisting of methylol compounds ethersof said methylol compounds with low-molecular aliphatic alcohols havingat most 4 C-atoms,

(b) An aliphatic compound which contains a carbon chain of at least 7C-atoms selected from the group consisting of Mono-carboxylic acids,Mono-carboxylic acid-N-methylolamides and N-methylol-urethanes, and

(c) A low-molecular tertiary amine which contains a reactive hydrogenatom attached to oxygen,

and the resulting basic products are then converted into water-solublesalts, including quarternary ammonium salts.

The process can be carried out in such a manner that first the compoundsspecified under (a) are condensed with the compounds as specified under(b) and the condensation product thus obtained reacted with thecompounds as specified under (0), or that first the components specified under (a) and (c) are combined and the product obtained reactedwith the compounds specified under (b), or further that first thecompounds specified under (b) and (c) are condensed together and thecondensation product thereupon reacted with the compounds as specifiedunder (a). Finally the possibility is also provided of reacting allthree components together simultaneously.

As methylol compounds of amino-1:3:5-triazines which may be used asreaction components corresponding to (a) there are primarily concernedthe reaction products of formaldehyde with2:4:6-triamino-1:3z5-triazine, usually known as melamine. Suchcondensation products can contain from 1 to 6 methylol groups and theyusually constitute mixtures of difierent compounds. Furthermore,methylol compounds are concerned of such derivatives of melamine asstill contain at least one amino group, for example methylol compoundsof melam, melem, ammeline, ammelide or of halogen substitutedamino-1:3:5- triazines, such as 2-chloro-4:6-diamino-l23:5-triazine;moreover methylol compounds of guanamines, as for example ofbenzoguanamine, acetoguanamine or formo guanamine.

The ethers of the methylolamino-l:3:S-triazines with low molecularalcohols, which are applicable, can be derived from the compounds justmentioned on the one hand and from aliphatic alcohols having at most 4C-atoms on the other hand, for example from methyl alcohol, butylalcohol or allylalcohol. There may be mentioned, for example, the methylethers of methylolof amino-1 :3 S-triazines and 2,864,781 Patented Dec.16, 1958 melamines with 4 to 6 methylol groups in which 2 to 6 methylolgroups are etherified. Such ethers can be obtained, for example, byheating of the methylol melamines with the alcohols in the presence ofsmall quantities of mineral acids in the conventional manner.

The aliphatic compounds which contain a carbon chain or" at least 7C-atoms and which can be used as reaction components corresponding to(b) are mono-carboxylic acid, mono-carboxylic acid-N-methylolamides andN- methylol urethanes. Among the mono-carboxylic acids having a carbonchainof at least 7 C-atoms there may be mentioned, for example, capric,lauric, myristic, palmitic, oleic, stearic, behenic, ricinoleic andmontanic acids and similar acids such as the mixtures of acids derivedfrom vegetable or animal fats and oils, for instance coconut oil or palmkernel oil.

The mono-carboxylic acid N-methylolamides which can be used for thepresent process may be the N-methyl olamides of the aforesaidmono-carboxylic acids; but the methylol derivatives of any otheraliphatic mono carboxylic acid amide having a carbon chain of at least 7C-atoms may be employed for this purpose.

Among the aliphatic N-methylol-urethanes which contain a carbon chain ofat least 7 C-atoms and which can also be used as reaction components(12) there may be mentioned N-methylolurethanes such, for example, asN-methylol-dodecylurethane, N-methylol-heptadecyl-urethane andN-methylol-octadecylurethane.

Among the specified, compounds which can be employed as reactioncomponents corresponding to (b) preferably such are used as contain acarbon chain of l6-l8 C-atoms,

for example, stearic acid, stearic acid-N-methylolamide.

and N-methylol-octadecylurethane.

The low-molecular tertiary amines which contain a reactive hydrogen atomattached to oxygen and which are to be used as components correspondingto (0) may belong to the heterocyclic or preferably to the aliphaticseries. There may be mentioned low-molecular monotertiary alkanolaminessuch, for example, as ,B-oxyethylmorpholine, methyl-diethanolamine,ethyl-diethanolamine, dimethyl-ethanolamine, diethyl-ethanolamine,diisopropyl-ethanolamine, tri-(iso)-propanolamine and especiallytriethanolamine.

Instead of the application of individual compounds which are set forthas reaction components under (a), (b) and (c) for the present process,obviously mixtures of several of such compounds can also be used.

The manufacture of the new ternary condensation products takes place, inpart, by the application of conventional processes, namely those whichare known for the synthesis of the binary intermediate products. Theproduction of condensation products from the com ponents (a) and (b) maybe illustrated by the reaction may be of advantage to have present inthe reaction an auxiliary solvent, such as benzene or toluene, whichrenders it possible to remove the water of reaction continuously fromthe reaction mixture in the form of an azeotropic mixture. Theproceedlng can, for example,

.. be such that the reaction is carried out at the boiling point of theauxiliary solvent and the distillate condensing in the reflux condenser,prior to return to the reaction vessel, is passed through a waterseparator which retains the water which has been split off. In a similarmanner, instead of the N-methylolamides, the reaction can be carried outwith the mono-carboxylic acids and N-methylol-urethanes which areconcerned as reaction components corresponding to (b).

The reaction of intermediate products thus produced with the reactioncomponent that is to say the lowmolecular tertiary amines defined abovelikewise takes place with advantage at elevated temperatures, preferablyat temperatures above 100 C., for example at 120-450". The reactingcompounds can simply be fused together or reacted in the presence of aninert organic solvent. It may be of advantage to carry out the reactionunder reduced pressure, whereby the easily volatile products produced,such as water and low molecularalcohols, can be removed from thereaction mixture.

The operations are similar when first the reaction components (a) and(c) are reacted together and the intermediate product produced iscondensed with the component (b), or when first a condensation productis produced from the compounds corresponding to (b) and (c) and this isfurther condensed with component (a), or when all three components arereacted together simultaneously.

The molecular ratio between the components which are used is primarilydependent upon the number of the methylol or methylol ether groups inthe component (a). Advantageously for one mol of a compoundcorresponding to (a) 1-2 mol of a compound corresponding to (b) and 1mol of a compound corresponding to (c) are used for the reaction.

The new products obtainable by the reaction sequences above set forthconstitute wax-like substances which as such are insoluble in water butin the form of salts are water-soluble.

The conversion of the free bases into the water-soluble salts, includingquaternary ammonium salts which follows the condensation, is conductedby per se conventional methods. For the salt formation, inorganic acidssuch, for example, as hydrochloric acid, sulfuric acid and phosphoricacids, or organic acids can be used. There'are employed advantageouslylow-molecular carboxylic acids such as formic acid, propionic acid,tartaric acid, lactic acid, oxalic acid, and especially acetic acid. Forthe conversion of the basic ternary condensation products intoquaternary ammonium salts dimethyl-sulfate or benzyl chloride issuitable, for example. Other quaternizing agents, such asepichlorhydrine and monochloroacetamide, may be used too.

The water-soluble salts obtainable according to the present invention,when prepared from suitable starting materials, can be used, among otherpurposes, as auxiliary substances, for example in the textile, leatherand paper industries. They can be applied as agents for renderingmaterials water-repellent and also as agents which reduce creasing orshrinking during washing and especially as softening agents. Upon woolinteresting finishing effects can be attained with suitable productsobtainable according to the invention, especially a considerablyincreased resistance to shrinkage, combined with an agreeable softhandle.

The application of the products obtainable according to the presentprocess can be carried out in such a manner that the materials to beimproved, preferably textiles, are treated with solutions,advantageously aqueous solutions of salts of the ternary condensationproducts, and if desired are heated to elevated temperatures.

For the finishing of wool, the material can be treated, for example,with a 510 percent aqueous solution of a salt of a product of theprocess, dried at low temperature and then heated for some time, forexample 2 hours, to 80-90 C. In this manner, with products which containan aliphatic radical with about 16-18 C-atoms, especially valuablefinishes are obtained.

For the finishing of cellulosic materials, such as cotton or artificialsilk from regenerated cellulose, the materials, impregnated with aqueoussolutions of salts of suitable products of the process, advantageouslyin the presence of excess of acid such as formic acid, after pressing orsqueezing out, can, without intermediate drying, be heated to elevatedtemperature, for example to 100-150" C. In this method of treatment,products with an aliphatic radical of about l618 C-atoms impart to thetreated material a water-repellent finish which is to a far-reachingextent resistant to washing. To the baths intended for the production ofa water-repellent finish there may be added water-soluble aluminiumsalts, for example aluminium triformate, or also zirconium compounds,for example zirconium salts or sols of hydrated zirconium dioxide, orparaffin wax dispersions. In a similar manner a soft handle can also beimparted to the textiles. For the preparation of a water-repellentfinish in general 1080 grams per liter of the condensation products areadded to the foularding bath, Whereas for imparting a soft handle muchsmaller quantities, for example 0.1 percent of the weight of the fabric,are sufficient.

The products of the present invention can be used alone or, as to someextent already indicated, together with other substances, such as salts,especially of weak acids, for example sodium acetate or aluminiumacetate, or also together with hydrocarbons, such as paraffin Wax,solvents, methylolamides, protective colloids, finishing or mattingagents, such as methylolureas, weighting or softening agents and thelike, these additions being, however, selected in such a manner thatthey cause no precipitation of the products of this invention from thesolutions of their salts.

The following examples illustrate the invention, the parts being byweight unless otherwise stated and the relation between part by weightand part by volume being the same as that between the kilogram and theliter:

Example 1 A mixture of 15 parts of triethanolamine and 90 parts of afused ester from methylated methylolmelamine and stearic acid, thepreparation of which is described below, is heated with stirring, underreduced pressure 10-20 mm.) to 1l5l20 C. until a test portion removedfrom the reaction vessel is soluble in dilute hot acetic acid. Thereuponthe melt is stirred at 7080 C. with 7 parts of glacial acetic acid. Ayellowish, wax-like and watersoluble product is obtained which onstirring with about double the quantity of hot water assumes apaste-like consistency.

The ester from the methylated methylol melamine and the stearic acid isprepared in an analogous manner to the esters described in Swiss patentspecification No. 251,642. In this process, however, there is used asstarting material a methylated methylol melamine which only differs fromthe methylol melamine methyl ether described in the last paragraph ofthe example of the said specification by the fact that the syrup whichis obtained after condensation, filtration and concentration to about 99percent, is not taken up in benzene but filtered hot for the removal ofthe residual salt.

1 part of this methylol melamine methyl ether is heated with about 1.3parts of stearic acid under a pressure of 10-20 mm. to l200 C. until theacid number of the product has fallen to 5-8.

When 102 parts of the basic condensation product, ob tainable accordingto the first paragraph of this example and not neutralized with aceticacid, are stirred at 60-70" C. with 8.9 parts of propionic acid, awax-like product is obtained which is soluble in water.

Example 2 A mixture of 15 parts of triethanolamine and 90 parts of afused condensation product from methylated methylol melamine andN-methylol stearic acid amide, the preparation of which is describedbelow is heated with stirring at a reduced pressure of -20 mm. for onehour to 115120 C. The basic condensation product thus obtained, whichdissolves in hot dilute acetic acid, is treated at 90 C. with 7 parts ofglacial acetic acid and the mixture well stirred for one hour. Afterallowing to cool, a wax-like, water-soluble mass is obtained.

When 102 parts of the aforesaid basic condensation produced are stirredat 70 C. with 120 parts of glycolic acid of 70 percent strength and 186parts of water of 70 C., a paste is obtained, which can be diluted withwater.

The condensation product from the methylated methylol melamine and theN-methylol stearic acid amide, is prepared by heating a mixture of 60parts of N-methylol stearic acid amide and 39 parts of the methylolmelamine methyl ether described in Example 1, to 115-120 C. for 1-2hours at a pressure of 10-20 mm. A hard waxlike mass is obtained, givinga, clear melt with paraflin wax but being itself unmelted in a boilingwater bath.

Example 3 parts of triethanolamine and 39 parts of the methylol melaminemethyl ether mentioned in Example 1, are heated under a pressure of10-20 mm. for one hour to 115120 C. Thereupon, at 115120 C. withstirring, 60 parts of N-methylol-stearic acid amide are introduced insmall portions. After the whole is fused together, the pressure in thereaction vessel is reduced to 1020 mm. and the melt intensively stirredfor one to two hours at 115-120. Thereupon 7 parts of glacial aceticacid are added at 90-95 C. and the melt stirred for one hour at 80-90 C.under atmospheric pressure. The condensation product obtained possessesproperties similar to that produced according to Example 2.

Example 4 15 parts of triethanolamine and 90 parts of a condensationproduct from N-methylol stearic acid amide and an etherification productfrom hexamethylol melamine and methanol, which product contains about 3methoxy groups and is produced according to Example 1 of Swiss patentspecification No. 268,532, are fused together and, when a melt isproduced, heated with stirring at a pressure of 10-15 mm. for 3 hours to115120 C. A viscous melt is obtained which, after completesolidification, can be pulverised and which is soluble to a clearsolution in hot dilute acetic acid.

The basic condensation product forms opalescent solutions with hotaqueous solutions of oxalic acid, tartaric acid, phosphoric acid andsodium dihydrogen phosphate.

Example 5 27 parts of commercial stearic acid and 36 parts of the highlymethylated methylol melamine specified in Example 1 are fused in areaction vessel and heated under a reduced pressure, initially of 50 mm.depending on the degree of foaming, in 2 hours to 190200 C. Afterstirring for one hour at this temperature, the whole is allowed to coolto 120 C. and 30 parts of N-methylol stearic acid amide are introduced.After melting of the methylol amide the whole is intensively stirred at115l20 C. for one hour at a reduced pressure of 10-20 mm. The product,which solidifies on cooling to a wax-like mass, melts in the hot waterbath and forms a clear melt in paraffin wax. The condensation productobtained in this manner can be condensed in an analogous manner to thatdescribed in Example 1 with, for example, 15 parts of triethanolamineand after conversion of the product into the acetic acid salt a mass isobtained which is soluble in hot water. I

6 Example 6 By proceeding exactly as described in Example 2, with theexception that instead of the 60 parts of N-methyiolstearic acid amide68 parts of N-methylol octadecylurethane, prepared fromoctadecylurethane and formaldehyde by conventional methods, are used,- asoft and waxlike mass which is easily soluble in hot water is obtained.

Example 7 27 parts of commercial stearic acid and 15 parts oftriethanolamine are heated in a current of nitrogen at 180-200 .C. untila test portion of the melt forms a clear solution in hot dilute aceticacid. Thereupon 36 parts of the methylol melamine methyl ether specifiedin Example 1 are added at 120 C. and the reaction mixture stirred for 2hours under a pressure of 30 mm. at 1l5120 C. 30 parts of N-methylolstearic acid amide are then further added and the melt maintained at115120 C. under a reduced pressure of 30 mm. until a test portion isentirely soluble in hot dilute acetic acid, which is usually the caseafter an hour. The melt is now allowed to cool to C. and 6.5 parts ofglacial acetic acid added. After thorough stirring for one hour waxlikemass is obtained which is soluble in hot water.

Example 8 30 parts of N-methylol stearic acid amide, 0.5 part of dry,powdered sodium carbonate and 15 parts of triethanolamine are fusedtogether under a reduced pressure of 30 mm. and heated for 2 hours to C.The melt is then soluble in dilute acetic acid. It is mixed with 36parts of the methylol melamine methyl ether specified in Example 1 andthe mixture again heated under re duced pressure to C. After 2 hours afurther 30 parts of N-methylol stearic acid amide are added andthe'stirring continued until a test portion is soluble in dilute aceticacid. When this is the case, the whole is allowed to cool to 90 C. and 6parts of glacial acetic acid added. After a further hours stirring atatmospheric; pressure, the melt is allowed to solidify to a wax-likemass which is soluble in hot water.

When the basic condensation product, obtained accord ing to thepreceding paragraph but not neutralized with acetic acid, is stirred at7080 C. with 13 parts of freshly distilled dimethylsulfate, a wax-likemass is obtained which is soluble in warm water of acid or alkalinereaction.

When the basic condensation product, obtained according to the firstparagraph of this example but not neutralized with acetic acid, isstirred for 46 hours with 13 parts of benzyl chloride at 85-l05 C.,there is obtained a product which is soluble in hot water.

The quaternary ammonium salts described above can be used as softeningagents. The softening effect obtained therewith on viscose rayon is fastto washing when the material treated in the presence of an acid catalystis subjected, after drying, to a heat treatment at C. for 5 minutes.

Example 9 14 parts of N-hydroxyethyl-morpholine and 90 parts of theester from methylated methylol melamine and stearic acid mentioned inthe second paragraph of Example 1 are fused together and the melt heatedto 120 C. while stirring under a pressure of 20-30 mm. After 3-4 hours atest portion is soluble in warm dilute acetic acid. Themelt is cooled to60 C. and 13 parts offreshly distilled neutral dimethyl sulfate addeddropwise, after which the product is stirred for another hour at 5060 C.On cooling, the viscous melt solidifies to form a hard, wax-like mass ofpale yellow color which is soluble in warm water.

Example 10 56 parts of cocoanut oil fatty acid and 55 parts of thehighly methylated methylol melamine mentioned in Example 1 are fusedtogether in a flask and heated to 195-200 C. in the course of 2 hoursunder in initial pressure of 10-50 mm., depending on the degree offoaming. The melt is stirred for two hours at this temperature and thenallowed to cool to 120 C., and 23.5 parts of triethanolamine added. Thereaction mass is then heated to 115-120 C. for an hour and a half at10-15 mm. pressure. When the melt is stirred with 9 parts of glacialacetic acid at 80 C. there is obtained a red-brown, clear oil which issoluble in water.

Example 11 Cotton gabardine is treated on the foulard up to an increasein weight of about 100 percent, in an aqueous bath at a temperature of60-65" C. which contains 9 parts of water, 0.1 part of ammoniumchloride, 0.1 part of 85 percent formic acid and 0.8 part of theemulsion described below. The fabric is thereupon dried at 80 C. andsubsequently after-treated for minutes at 120-150 C. Both the unwashedand the washed fabric shows good water-repellent properties.

The emulsion used in this example can be produced as follows:

40 parts of the product obtainable according to EX- ample 1 and 40 partsof paraflin wax are melted together at 90-95 C. Emulsification withbrisk stirring is then carried out with the addition of 80 parts ofwater at 60-70 C. The emulsion is continuously stirred until the massreaches room temperature.

Example 12 An operation is conducted in an analogous manner to thatdescribed in Example 11 but using a bath which contains 9 parts ofwater, 0.1 part of ammonium chloride, 0.1 part of 85 percent formic acidand 0.1-0.8 part of one of the condensation products obtainableaccording to Examples 1, 2, 3, 5, or 6. In this manner a cottongabardine is obtained which possesses a finish of good water-repellentproperties which are still retained after a boiling wash with 5 gramsper liter of soap and 2 grams per liter of sodium carbonate.

Example 13 Viscose artificial silk is treated for 30 minutes at 20-30 C.with a bath ratio of 1:30 in a bath which contains 0.1-1 percent of oneof the condensation products obtainable according to Examples 1-9 and1-4 percent of ammonium chloride (both calculated upon the weight ofyarn). Drying is then carried out at 80 C. and hardening at a somewhathigher temperature. A viscose artificial silk is obtained with a verygood, soft handle which still remains after washing A hour at 90 C. in abath which contains 2 grams per liter of the disodium salt ofZ-heptadecyl-N-benzylbenzimidazole disulfonic acid and 1 gram per literof 25 percent ammonia).

Example 14 A mixture of 20 parts of tri-isopropanolamine and 90 parts ofthe ester from methylated methylolmelamine and stearic acid, thepreparation of which is described in Example 1, is heated with stirringunder reduced pressure (-20 mm.) to 115120 C. until a test portionremoved from the reaction vessel is soluble in dilute hot acetic acid.Thereupon the melt is stirred at 60-70 C. with 7 parts of glacial aceticacid. A yellow-brown, wax-like and water-soluble product is obtained.The product gives foaming stable solutions in hot diluted acetic acid.

Example 15 90 parts of the ester from methylated methylolmelamine andstearic acid, the preparation of which is described in Example 1, and 9parts of dimethyl-ethanolamine are heated for two hours to 135-140 C.,whereupon a test portion removed from the reaction mixture is soluble in8 dilute hot acetic acid giving a foaming solution on shaking. The basiccondensation product thus obtained is then stirred at 60 C. with 7 partsof glacial acetic acid. After allowing to cool, a Wax-like,water-soluble and weakly yellow colored mass is obtained.

Example 16 Example 17 The process is conducted as described in Example 8but the -36 parts of r'nethylolmelamine methyl ether used therein arereplaced by 50 parts of a hexamethylolmelamine allyl ether having 4-6allyl ether groups or by 58 parts of a hexamethylolmelamine butyl etherhaving 4-6 butyl ether groups. In. both cases wax-like products areobtained, the solutions of which foam on shaking.

What is claimed is:

1. A water-soluble salt of a hardenable basic ternary condensationproduct which has been obtained by heating together first (a) an etherof a methylol-melamine with a low-molecular aliphatic alcohol having atmost 4 C-atoms, with (c) triethanolamine, and then heating thecondensation product so obtained with (b) a member selected from thegroup consisting of monocarboxylic acids of the formula I R-COOHmonocarboxylic acid-N-methylolamides of the formula RCO-NHCH OH andN-methylol-urethanes of the formula ROCONH-CH OH in which formulae Rstands for an aliphatic hydrocarbon radical with 7 to 18 carbon atoms,and converting the basic product into the water-soluble salt.

2. A water-soluble salt of a harden'able basic ternary condensationproduct which has been obtained by heating together first (a) about 1mol of a hexamethylolmelamine hexamethyl ether with (b) about 2 mols ofstearic acid in vacuo to ISO-200 C., and heating the ester thus obtainedwith (c) about 1 mol of triethanolamine in vacuo to -120 C. until theproduct is soluble in dilute acetic acid, and converting the base intothe watersoluble salt with propionic acid.

3. A Water-soluble salt of a hardenable basic ternary condensationproduct which has been obtained by heating together first (a) about 1mol of a hexamethylolmelamine hexamethyl ether with (b) about 2 mols ofN-methylol octadecylurethane in vacuo to 115-120 C. for 1-2 hours, andheating the ether thus obtained with (0) about 1 mol oftriethanolaminein vacuo to 115-120 C. for one hour, and converting the base into thewater-soluble salt with acetic acid.

4. A water-soluble quaternary ammonium salt of a hardenable basicternary condensation product which has been obtained by heating togetherfirst (b) 1 mol of stearic acid N-methylolamide with (c) 1 mol oftriethanolamine at 110 C. for two hours in vacuo, heating the amide thusobtained with (a) 1 mol of a hexamethylolmelamine hexamethyl ether at C.for two hours in vacuo and heating this condensation product withanother mol of stearic acid N-methylolarnide until the product issoluble in dilute acetic acid, and finally converting the base into thequaternary ammonium salt with 1 mol of dimethyl sulfate at 7080 C. atordinary pressure.

9 1o 5. A water-soluble salt of a hardenable basic ternary acetic acid,and converting the base into the water-solucondensation product whichhas been obtained by heat- 'ble salt with acetic acid.

ing together first (a) about 1 mol of a hexamethylolmelamine hexamethylether with (b) about 2 mols of stearic References Clted 111 the filfi of1115 Patent acid in vacuo to 180-200 C., and heating the ester thus 5UNITED STATES PATENTS obtained with (c) about 1 mol oftri-isopropanolamine in vacuo to 115-120 C. until the product is solublein dilute 2783231 Albrecht et a1 1957 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 2,864,781 December 16, 1958 In theheading to the printed specification, between lines 8 and 9 thereof,insert Claims priority, application Switzerland August 31, 1951 column6, line 24, after "hour" insert a column 7, line 3, for "in initial"read an initial Signed and sealed this 7th day of July 1959.

(SEAL) Attest:

KARL AXLINE I ROBERT c. WATSON Attesting Officer Conmissioner of Patents

1. A WATER-SOLUBLE SALT OF A HARDENABLE BASIC TERNARY CONDENSATIONPRODUCT WHICH HAS BEEN OBTAINED BY HEATING TOGETHER FIRST (A) AN ETHEROF A METHYLOL-MELAMINE WITH A LOW-MOLECULAR ALIPHATIC ALCOHOL HAVING ATMOST 4 C-ATOMS WITH (C) TRIETHANOLAMINE, AND THEN HEATING THECONDENSATION PRODUCT SO OBTAINED WITH (B) A MEMBER SELECTED FROM THEGROUP CONSISTING OF MONOCARBOXYLIC ACIDS OF THE FORMULA